Liquid-based Solid Imaging, for example, Stereolithography, is a process whereby a photoformable liquid is applied as a thin layer to a surface and exposed to actinic radiation such that the liquid solidifies. Subsequently, new thin layers of photoformable liquids are coated onto previous layers of liquid or previously solidified sections. The new layers are then exposed imagewise in order to solidify portions imagewise and in order to induce adhesion between portions of the new hardened region and portions of the previously hardened region. Each imagewise exposure is of a shape that relates to a pertinent cross-section of a photohardened object such that when all the layers have been coated and all the exposures have been completed, an integral photohardened object can be removed from the surrounding liquid composition.
Photoformable resins currently used in generating the photohardened object generally contain a cationically polymerizable compound, such as an epoxy compound, and/or a radically polymerizable compound, such as an acrylate, together with cationic and/or radical photoinitiators. For example, JP 02075618A discloses a photocurable resin containing an epoxy, an acrylate, and an antimony-containing cationic photoinitiator and free radical photoinitiator.
Antimony is a toxic heavy metal and its presence in photohardened parts makes resins containing antimony less useful in many applications. In addition, because of their high reactivity, antimony hexafluoride salts are prone to instability and cause viscosity build-up in the resin over time. Removal of the cationically polymerizable compound so that the composition contains only radically polymerizable compounds is not an adequate solution since these resins produce objects having a much greater distortion due to acrylate shrinkage as well as insufficient green strength and brittleness. Adding stabilizers to the resin composition is also not an adequate solution since the stabilizers are consumed over time and must be continuously added to the resin in order to maintain a low viscosity.
Therefore, it would be desirable to produce a low viscosity, stable, antimony-free photocurable composition which can be cured rapidly in a liquid-based solid imaging process to produce an article having a high green strength, toughness, dimensional accuracy and minimal distortion.
Asahi Denka described the composition of hybrid epoxy acrylate formulations for laser imaging (JP 02075618A). This document teaches that cycloaliphatic epoxy resins combined with triaryl sulfonium antimony hexafluoride are the preferred epoxy-cationic initiator systems in optical molding systems. Commercial resins since this patent have used this same cationic initator as well as one or more other features of this patent. Subsequent patent disclosures have also focused on formulations using the antimony salt. The current disclosure shows surprisingly that certain formulations can now be developed which do not use the antimony hexafluoride salt.
Huntsman WO 03/089991 A2 describes SL resins containing reactive core shell particles, producing parts with smooth surfaces and good mechanical properties. In this patent, Huntsman uses triaryl sulfonium antimony hexafluoride salt as the cationic initiator. Reactive particles are stable and do not phase separate. In the current disclosure, formulations containing such reactive particules which, combined with a cationic photoinitiator that does not contain antimony hexafluoride, provide parts with improved and more balanced mechanical properties.
WO 03/093901 A1 describes the use of hydrogenated epoxy components in combinaison with oxetane components to give resins with “good water resistances”.
The current invention uses non-antimony containing initiator salts and describes novel compositions with broad range of acrylic content. Preferably, it was found that formulations with greater than 25% acrylate content, using cationic initiator that do not contain antimony hexafluoride, yields surprisingly good overall properties.
US2005/0228064 A1 describes the use of tougheners.
U.S. Pat. No. 6,811,937 describe use of low MW polyTHF with specific acrylates to obtain high clarity. Dipentaerythritol hexaacrylate is used, whereas we demonstrated a similar improvement using dipentaerythritol pentaacrylate in our PF6 formulation. Preferably, in the compositions according to the invention, the free radically active component does not comprise dipentaerythritol hexaacrylate.
U.S. Pat. No. 6,379,866 describe the use of a reactive toughener made of a single reactive toughener.
WO 2005/045525 describe the use of nanoparticules.